Anti-smudge agent, smudge proof coating composition, smudge proof film, and article coated with smudge proof film

• US 7,763,678 B2
• Filed: 04/12/2007
• Issued: 07/27/2010
• Est. Priority Date: 04/14/2006
• Status: Active Grant

• Current Assignee: Shin-Etsu Chemical Company Limited
• Original Assignee: Shin-Etsu Chemical Company Limited
• Inventors: Sato, Kazuharo, Yamaya, Masaaki
• Primary Examiner(s): Gulakowski; Randy
• Assistant Examiner(s): Negrelli; Kara
• Application Number:
  US11/783,846
• Publication Number:
  US 20070243394A1
• Time in Patent Office: 1,202 Days
• Field of Search: 524/588, 524/268, 524/4, 528/42, 528/36
• US Class Current: 524/588
• CPC Class Codes: C08G 77/24 halogen-containing groups
• CPC Class Codes: C08G 77/50 by carbon linkages C08G77/485 takes precedence
• CPC Class Codes: C09D 183/08 containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
• CPC Class Codes: C09D 183/14 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms C09D183/10 takes precedence
• CPC Class Codes: G02B 1/18 Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films G02B1/16 takes precedence
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

An anti-smudge agent which is added to a coating composition for imparting smudge proof property with the coating composition, comprising a silicone resin containing a fluorine atom-containing organic group, which has a number average molecular weight of at least 1,000 and a molar ratio of the fluorine atom to the silicon atom (F/Si) of 3 to 50, said silicone resin being produced by hydrolyzing or condensing an organosilicon compound having a fluorine atom-containing organic group represented by the following general formula (I):
R¹R²_mSiX_3−m  (I)
wherein R¹ is a fluorine atom-containing organic substituent, R² is a substituted or unsubstituted alkyl group or phenyl group containing 1 to 10 carbon atoms, X is a hydrolyzable group or OH group, and m is 0 or 1; or a hydrolysate or a partial condensate thereof.

Claims

1. A smudge proof coating composition which is a dispersion in an organic solvent of

(1) 0.01 to 10% by weight of an anti-smudge agent comprising a silicone resin containing a fluorine atom-containing organic group, which has a number average molecular weight of at least 1,000 and a molar ratio of the fluorine atom to the silicon atom (F/Si) of 3 to 50;

said silicone resin being the one produced by hydrolyzing or condensing an organosilicon compound having a fluorine atom-containing organic group represented by the following general formula (I);

R¹R²_mSiX<sub>3−

m</sub> 

 

(II

wherein R¹ is a fluorine atom-containing organic substituent, R² is a substituted or unsubstituted alkyl group or phenyl group containing 1 to 10 carbon atoms, X is a hydrolyzable group or OH group, and m is 0 or 1;

or a hydrolysate or a partial condensate thereof; and

(2) 99.99 to 90% by weight of a condensation curable silicone resin.

2. A smudge proof coating composition according to claim 1 wherein the condensation curable silicone resin (2) is a silicone resin which is not completely compatible with the anti-smudge agent (1) in the absence of the organic solvent.

3. A smudge proof coating composition according to claim 1 wherein the condensation curable silicone resin is the one produced by hydrolyzing and condensing the silane compound containing

X₃₋

pR²_pSi—

R³—

SiR²_qX<sub>3−

q</sub> 

 

(III)

wherein R² and X are as described above, R³ is —

O—

, —

(CH₂)_r—

, —

C₆H₄—

, or a fluorine-substituted divalent organic group, p and q are independently 0, 1, or 2; and

r is an integer of 1 to 6;

or a hydrolysate or a partial condensate thereof.

4. A smudge proof coating composition according to claim 1 further comprising an inorganic material which is selected from inorganic oxide fine particles and hollow and/or porous inorganic oxide fine particles.

7. A coated article wherein the smudge proof coating composition of claim 1 has been coated and cured as the outermost layer of the article.

8. A coated article according to claim 7 wherein the substrate comprises a plastic, a metal, or a ceramic.

9. A smudge proof coating composition according to claim 1 wherein the silicone resin of the anti-smudge agent is the one produced by hydrolyzing or condensing a silane compound comprising

(i) 50 to 100% by weight of an organosilicon compound represented by the general formula (I):

R¹R²_mSiX<sub>3−

m</sub> 

 

(I)

wherein R¹ is a fluorine atom-containing organic substituent, R² is a substituted or an unsubstituted alkyl group or phenyl group containing 1 to 10 carbon atoms, X is a hydrolyzable group or OH group, and m is 0 or 1;

or a hydrolysate or a partial condensate thereof;

(ii) 50 to 0% by weight of an organosilicon compound represented by the general formula (II) and/or (III);

R²_nSiX<sub>4−

n</sub> 

 

(II)

X<sub>3−

p</sub>R²_pSi—

R³—

SiR²_qX<sub>3−

q</sub> 

 

(III)

wherein R² and X are as described above, R³ is —

O—

, —

(CH₂)_r—

, —

C₆H₄—

, or a fluorine-substituted divalent organic group, n, p, and q are independently 0, 1, or 2; and

r is an integer of 1 to 6;

or a hydrolysate or a partial condensate thereof.

10. A smudge proof coating composition according to claim 1 wherein the organosilicon compound represented by general formula (I) is

F(CF₂)₈—

C₂H₄—

Si(OCH₃)₃.

5. A smudge proof film produced by coating and curing a smudge proof coating composition as the outermost layer of a substrate,

the smudge proof coating composition being a dispersion in an organic solvent of

(1) 0.01 to 10% by weight of an anti-smudge agent comprising a silicone resin containing a fluorine atom-containing organic group, which has a number average molecular weight of at least 1,000 and a molar ratio of the fluorine atom to the silicon atom (F/Si) of 3 to 50;

said silicone resin being the one produced by hydrolyzing or condensing an organosilicon compound having a fluorine atom-containing organic group represented by the following general formula (I);

R¹R²_mSiX<sub>3−

m</sub> 

 

(I)

wherein R¹ is a fluorine atom-containing organic substituent. R² is a substituted or unsubstituted alkyl group or phenyl group containing 1 to 10 carbon atoms, X is a hydrolyzable group or OH group, and m is 0 or 1;

or a hydrolysate or a partial condensate thereof; and

(2) 99.99 to 90% by weight of a condensation curable silicone resin,

wherein said anti-smudge agent is predominantly present on the surface side of the cured film.

6. A smudge proof film according claim 5 wherein the smudge proof film has a contact angle with oleic acid of at least 60°

.